CN113437225B - Perovskite solar cell modified by photonic crystal and preparation method thereof - Google Patents
Perovskite solar cell modified by photonic crystal and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a perovskite solar cell modified by photonic crystals, which sequentially comprises a transparent electrode, an electron transmission layer, a perovskite layer, a hole transmission layer and a counter electrode from top to bottom, and is also provided with a packaging structure, the perovskite solar cell also comprises a photonic crystal layer, the photonic crystal layer is arranged between the transparent electrode and the electron transmission layer, the defect of a mesoporous structure is improved by utilizing the photonic crystal structure, the light absorption capacity of the perovskite layer is improved, and the utilization rate of a light source can also be improved, so that the cell has the characteristics of high light absorption coefficient, high photon-generated carrier separation efficiency, low defect density, high photoelectric conversion efficiency and good stability. The invention also discloses a preparation method of the perovskite solar cell modified by the photonic crystal, the photonic crystal layer film body prepared by the evaporation method is uniform and compact, and the photonic crystal material with larger area can be prepared, can be applied to optical devices and has wide application prospect.
Description
Technical Field
The invention relates to the field of perovskite solar cells, in particular to a perovskite solar cell modified by photonic crystals and a preparation method thereof.
Background
Since the 2009 Miyasaka team applies perovskite materials to solar cells for the first time, perovskite photovoltaic cells can be used as substitutes of silicon-based solar cells due to the advantages of high photoelectric conversion efficiency, abundant raw material reserves, low temperature, low cost preparation process and the like. In recent years, a series of results have been obtained in improving the preparation method.
As a representative semiconductor material, a perovskite material is an organic/inorganic hybrid special photoelectric material, which has the advantages of high light absorption coefficient, high carrier mobility, simple synthesis method and the like, but the defects of the perovskite and the problem of carrier recombination at the device interface always restrict the development of the perovskite solar cell. In a traditional perovskite battery, a photogenerated carrier of a perovskite light absorption layer reaches a carrier transmission layer in a diffusion mode to finish the collection and the transmission of the photogenerated carrier, the separation probability and the transmission rate of the photogenerated carrier are low, and the perovskite material is unstable, so that more non-radiative recombination centers (such as crystal boundaries, defects and the like) exist when the perovskite material is used as the light absorption layer, the recombination loss of the photogenerated carrier is easily caused, the recombination probability of the photogenerated carrier is further aggravated by the slow diffusion rate of the photogenerated carrier, and the photoelectric conversion efficiency of the perovskite solar battery is reduced. And the photon-generated carriers of the perovskite light absorption layer reach the carrier transmission layer in a diffusion mode, the transport is realized through the energy level matching between the perovskite light absorption layer and the carrier transmission layer, but the potential barrier band step at the interface of the carrier transmission layer and the perovskite light absorption layer is larger, the transport of the photon-generated carriers is hindered, the recombination loss probability of the photon-generated carriers is increased, and the photoelectric conversion efficiency of the perovskite solar cell is further reduced.
At present, some technologies for depositing a nanocrystal interface layer between a perovskite light absorption layer and a hole transport layer exist, however, although the technologies can passivate an interface to a certain extent, reduce the density of interface defects, and improve the light utilization rate of light from a perovskite layer transport layer to the perovskite layer, the technologies cannot fully utilize a light source, so that a large amount of light energy is wasted, and the photoelectric efficiency cannot be improved fundamentally.
Disclosure of Invention
The invention aims to overcome at least one defect (deficiency) of the prior art and provides a perovskite solar cell modified by photonic crystals and a preparation method thereof, the defect of a mesoporous structure is improved by utilizing the photonic crystal structure, the light absorption capacity of a perovskite layer is improved, and the utilization rate of a light source can also be improved, so that the cell has the characteristics of high light absorption coefficient, high separation efficiency of photogenerated carriers, low defect density, high photoelectric conversion efficiency and good stability.
The technical scheme adopted by the invention is that the perovskite solar cell modified by the photonic crystal is provided, the perovskite solar cell sequentially comprises a transparent electrode, an electron transmission layer, a perovskite layer, a hole transmission layer and a counter electrode from top to bottom, a packaging structure is further arranged outside the perovskite solar cell, the perovskite solar cell further comprises a photonic crystal layer, and the photonic crystal layer is arranged between the transparent electrode and the electron transmission layer.
Further, the electron transport layer is of a mesoporous framework structure.
Further, the material of the photonic crystal layer is polystyrene photonic crystal; the interior of the photonic crystal layer is of a honeycomb structure.
In the technical scheme, the photonic crystal layer is arranged between the transparent electrode and the electron transmission layer, the polystyrene photonic crystal can improve the quality of a mesoporous framework of the electron transmission layer, such as improving the particle size, the film thickness, the porosity and the like in the electron transmission layer, thereby reducing the defect density of the perovskite film, regulating and controlling the film forming quality of the perovskite layer, improving the quality and the stability of the perovskite layer, being more beneficial to improving the light absorption capacity of the perovskite layer and improving the light absorption coefficient and the separation efficiency of photogenerated carriers, in addition, the photonic crystal layer forms a honeycomb structure by using the polystyrene photonic crystal, compared with the existing modification layer arranged between the perovskite layer and the hole transmission layer, the existing modification layer improves the light utilization rate of light from the perovskite layer to the hole transmission layer, but only improves the utilization rate of light entering the battery, when the light source is a scattering light source, less light reaches the electron transmission layer, so that the photoelectric conversion efficiency is still not ideal at the moment, and the honeycomb structure of the photonic crystal layer can ensure that light rays emitted by the scattering light source pass through the transparent electrode and are reflected and refracted for multiple times in holes of the honeycomb structure to reach the electron transmission layer, so that the effect of enhancing the luminous intensity is achieved, the utilization rate of the light source is improved, and the photoelectric conversion efficiency is improved fundamentally.
Furthermore, the transparent electrode is made of a base material doped with ITO, FTO, AZO and ATO, and the electron transport layer is made of SnO2、TiO2、Nb2OS、SnO2、WO3、SrTiO3And Zn2SnO4The material of the perovskite layer is FAPBI3、MAPbI3The material of the hole transport layer isSpiro-OMeTAD、CuI、CuSCN、NiO、CuO、Cu2O、CuGaO2、Cu2NiOx、FeS2、MoS2、WS2、TiS2、Mg2Li2NiO, and the counter electrode is made of Au, Ag and Al.
Preferably, the transparent electrode is made of a doped Indium Tin Oxide (ITO) substrate material, and the electron transport layer is made of SnO2The material of the perovskite layer is FAPbI3The material of the hole transport layer is Spiro-OMeTAD, and the material of the counter electrode is Au.
In the technical scheme, SnO is adopted2As a material for the electron transport layer, the electron transport rate is higher, however, if SnO2When the photonic crystal layer is arranged between the transparent electrode and the electron transmission layer, the electron transmission layer can be modified, and SnO is avoided2The particles are too small, so that the electron transmission is promoted, the recombination rate is reduced, and the photoelectric conversion efficiency of the cell is improved.
The invention also provides a preparation method of the perovskite solar cell modified by the photonic crystal, which comprises the following steps:
s1 etching and ultrasonically cleaning the transparent electrode;
s2 preparing a photonic crystal layer on the transparent electrode processed at step S1;
s3 preparing an electron transport layer on the transparent electrode processed at step S2;
s4 preparing a perovskite layer on the electron transport layer prepared in step S3;
s5 preparing a hole transport layer on the perovskite layer prepared at step S4;
s6 a counter electrode was prepared on the hole transport layer prepared at step S5 using a thermal evaporation method.
Further, the step S1 is: and after etching the transparent electrode, immersing the transparent electrode in isopropanol, carrying out ultrasonic cleaning for 20-30 min, taking out, adding a detergent and deionized water, carrying out ultrasonic cleaning for 20-30 min, taking out, adding deionized water, carrying out ultrasonic cleaning for 20-30 min, repeatedly cleaning for 2-3 times, and drying for 12 h.
Preferably, the ultrasonic power of the ultrasonic cleaning is 40-60%, and the ultrasonic temperature is 20-25 DEG C
Preferably, in step S1, a specific position of the transparent electrode is etched, specifically, areas with the same width are etched on both sides of the transparent electrode, so as to distinguish the conductive surface from the non-conductive surface in the subsequent spin coating process, thereby avoiding misoperation.
Further, the step S2 is: soaking the transparent electrode treated in the step S1 in a piranha solution for 1-2 h, washing, drying in an inert gas environment, putting into a suspension of polystyrene monodisperse spheres dispersed in absolute ethyl alcohol, heating at 50-60 ℃ for 12-15 h until volatile matters in the suspension are completely evaporated, and preparing a photonic crystal layer on the transparent electrode; the piranha solution is a mixed solution of concentrated sulfuric acid and hydrogen peroxide solution, and the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide solution is (3-6): 1; the volume ratio of the polystyrene monodisperse spheres to the absolute ethyl alcohol in the suspension is (3-5): 8.
Preferably, the concentration of the concentrated sulfuric acid is greater than 95%, and the concentration of the hydrogen peroxide solution is 30%.
Preferably, the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide solution is 4:1, and the volume ratio of the polystyrene monodisperse spheres to the absolute ethyl alcohol in the suspension is 5: 8.
Further, the step S3 is to perform ozone treatment on the transparent electrode treated in the step S2, and then 50-60 μ L of 10-15% wt SnO is dripped2And dropwise adding the solution onto the surface of the transparent electrode, spin-coating for 15-30 s at a spin-coating speed of 1000-3000 r/m, and annealing at 130-160 ℃ for 10-15 min to obtain the electron transport layer deposited on the photonic crystal layer on the transparent electrode.
Further, in the step S4, the transparent electrode processed in the step S3 is subjected to ozone treatment, then 50 to 60 μ L of perovskite precursor solution is dripped to one surface of the transparent electrode on which the electron transport layer is deposited, spin coating is performed at a spin coating speed of 1000 to 3000r/m for 15 to 30S, 60 to 70 μ L of chlorobenzene is dripped on the surface of the transparent electrode before 5 to 8S of the completion of the spin coating, and after the completion of the spin coating, the transparent electrode is placed at 100 ℃ for annealing for 30min, wherein the perovskite layer is deposited on the electron transport layer of the transparent electrode.
Still further, the perovskite precursor solution is prepared by the following method:
mixing lead iodide powder, cesium iodide powder and FAI powder according to a mass ratio of (30-40) to (0-1) to (8-11) to obtain a powder mixture, mixing anhydrous DMSO and anhydrous DMF according to a volume ratio of (1-2) to (4) to obtain a mixed solution, mixing the powder mixture and the mixed solution 1 according to a mass ratio of (10-20), and heating the mixed solution for a period of time while stirring to obtain the perovskite precursor solution.
Preferably, the addition amount of the lead iodide is 0.3200-0.3260 g, the addition amount of the cesium iodide is 0.0080-0.0087 g, and the addition amount of the FAI is 0.1080-0.1089 g.
In step S5, a Spiro-OMeTAD precursor solution is dropped onto the transparent electrode processed in step S4, and spin-coating is performed at a rotation speed of 2000 to 4000r/m for 10 to 20 seconds, so that the hole transport layer is deposited on the perovskite layer of the transparent electrode.
Still further, the Spiro-OMeTAD precursor solution is prepared by the following method:
mixing Li-TFSI powder with acetonitrile to obtain a Li-TFSI solution with the concentration of 500-520 mg/ml, adding 4-tert-butylpyridine, the prepared Li-TFSI solution and chlorobenzene into the Spiro-OMeTAD powder, and uniformly stirring to obtain a Spiro-OMeTAD precursor solution; the mass ratio of the Li-TFSI powder to the Spiro-OMeTAD powder is (7-8): 1, and the volume ratio of the 4-tert-butylpyridine to the Li-TFSI solution to the chlorobenzene is (1-2): 1: (50-60).
Preferably, the addition amount of the Spiro-OMeTAD powder is 72.0-72.3 mg, the dropwise addition amount of the 4-tert-butylpyridine is 25-28.8 mu L, the dropwise addition amount of the Li-TFSI solution is 15-17.5 mu L, and the dropwise addition amount of the chlorobenzene is 1-2 ml.
Further, in step S6, after one electrode of the transparent electrode is scraped off and spin-coated, thermal evaporation is performed in vacuum at a rate of
And when the counter electrode is evaporated to reach the thickness of 80-100 nm, stopping evaporation, and cooling to obtain the perovskite solar cell modified by the photonic crystal.
Preferably, in the step S6, the transparent electrode is transferred to a vacuum thermal evaporation apparatus, placed in a mask plate, and scraped to remove one electrode that is spin-coated, and then placed in an evaporation machine, and vacuumized to below 106Torr for evaporation, and when the electrode is evaporated to a thickness of 80-100 nm, the evaporation is stopped, and the perovskite solar cell modified by the photonic crystal is obtained after cooling for 1 hour.
In this technical scheme, adopt the evaporation process to prepare the photonic crystal layer on transparent electrode, compare spin-coating method, its preparation simple process is high-efficient, wide application prospect has, can be in optical device, the photonic crystal layer film body of preparing through the evaporation process is even compact, and can prepare the photonic crystal material of bigger area, it can form honeycomb structure on transparent electrode, can reach electron transport layer through refraction reflection many times, play the effect of reinforcing luminous intensity, make the utilization ratio of light source obtain improving, and photonic crystal can also decorate electron transport layer, especially with SnO2The electronic transmission layer is made of the material, the quality of a mesoporous framework of the electronic transmission layer is improved, the defect density of the perovskite film is further reduced, the film forming quality of the perovskite layer is regulated and controlled, the quality and the stability of the perovskite layer are improved, the light absorption capacity of the perovskite layer is further improved, the transport of photon-generated carriers is promoted, and the photoelectric conversion efficiency can be further improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) the perovskite solar cell is modified by photonic crystals, so that the defect of the mesoporous skeleton quality of an electron transmission layer can be overcome, the defect density of a perovskite film is reduced, the film forming quality of a perovskite layer is regulated and controlled, the quality and the stability of the perovskite layer are improved, and the light absorption capacity and the photon-generated carrier separation efficiency of the perovskite layer are improved;
(2) the honeycomb structure of the photonic crystal layer of the perovskite solar cell can enable light rays emitted by a scattering light source to pass through the transparent electrode and then be refracted and reflected for multiple times in holes of the honeycomb structure to reach the electron transmission layer, so that the effect of enhancing the luminous intensity is achieved, the light energy is fully utilized, and the photoelectric conversion efficiency is improved fundamentally;
(3) the perovskite solar cell adopts SnO with higher electron migration rate2As an electron transport layer, SnO is made after the electron transport layer is modified by the photonic crystal layer2While the advantages of the photoelectric conversion device are kept, the phenomena of excessive crystal boundary, serious carrier recombination and serious hysteresis during use caused by too small particles are avoided, and the photoelectric conversion efficiency is improved;
(4) the perovskite solar cell preparation method adopts the evaporation method to prepare the photonic crystal layer on the transparent electrode, the preparation process is simple and efficient, and the prepared photonic crystal layer is uniform and compact, can be applied to optical devices and has wide application prospect.
Drawings
Fig. 1 is a schematic structural diagram of photonic crystal modified formamidine lead-iodine perovskite solar cells of examples 1 and 2.
Fig. 2 is a schematic diagram of an etching region of the transparent electrode in embodiments 1 to 3.
Fig. 3 is a graph showing the results of the photoelectric efficiency test of examples 1 to 3.
Fig. 4 is a scanning electron microscope image of the polystyrene photonic crystal layer of examples 1 and 2.
In the drawings are labeled: a transparent electrode 100; etching the region 110; a non-etched region 120; a photonic crystal layer 200; an electron transport layer 300; a perovskite layer 400; a hole transport layer 500; a counter electrode 600.
Detailed Description
The drawings are only for purposes of illustration and are not to be construed as limiting the invention. For the purpose of better illustrating the following embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the following embodiment, the transparent electrode is made of a substrate material doped with ITO, the etching regions 110 on both sides of the non-etching region 120 are etched according to fig. 2, and the electron transport layer is made of SnO2The material of the perovskite layer is FAPBI3The material of the hole transport layer is Spiro-OMeTAD, and the material of the counter electrode is Au.
Example 1
The embodiment provides a perovskite solar cell, which sequentially comprises a transparent electrode 100, an electron transport layer 300, a perovskite layer 400, a hole transport layer 500 and an electrode 600 from top to bottom, and the preparation method of the perovskite solar cell comprises the following steps:
s1, etching the transparent electrode by using a diamond pen according to the schematic diagram of the etching area of the figure 2, placing the transparent electrode on a polytetrafluoroethylene cleaning frame, then placing the etched transparent electrode and the polytetrafluoroethylene cleaning frame into a beaker, pouring isopropanol into the beaker until the transparent electrode is immersed, carrying out ultrasonic cleaning for 30min at the ultrasonic power of 40-60% at 20-25 ℃, then pouring out waste liquid, then adding detergent and deionized water, carrying out ultrasonic cleaning for 30min at the same ultrasonic power and temperature, then pouring out the waste liquid, adding deionized water, carrying out ultrasonic cleaning for 30min at the same ultrasonic power and temperature, repeatedly cleaning for 3 times, and then placing the electrode into a drying oven to dry for 12 h;
s2 the transparent electrode treated in step S1 was subjected to ozone treatment, and 1.5ml of 15% wt SnO2The solution was mixed with 6.5ml of deionized water to obtain SnO used for preparing electron transport layers2The transparent electrode after the ozone treatment is placed on a spin coater, the spin speed of the spin coater is set to 2000r/m, the spin time is set to 15s, and the spin acceleration is set to 500r/m260 mu L of SnO for preparing electron transport layer is dripped on the surface of the transparent electrode2Starting spin coating after the solution is dissolved, and heating the transparent electrode at 150 ℃ after the spin coating is finishedAnnealing for 15min on the platform, and depositing the electron transport layer on the transparent electrode;
s3, mixing 0.3260g of lead iodide powder, 0.0087g of cesium iodide powder and 0.1089g of FAI powder to obtain a powder mixture, mixing anhydrous DMSO and anhydrous DMF in a volume ratio of 1:4 to obtain a mixed solution, uniformly mixing 5.33ml of the mixed solution and the powder mixture, placing the mixed solution and the powder mixture at 70 ℃ while stirring and heating for 12 hours to obtain a perovskite precursor solution, and filtering the perovskite precursor solution through a filter head; subjecting the transparent electrode processed in step S2 to ozone treatment for 30min, placing on a spin coater in a glove box filled with Ar gas, setting the spin speed of the spin coater to 2000r/m, the spin time to 15S, and the spin acceleration to 500r/m2Absorbing 60 mu L of perovskite precursor solution by using a liquid transfer gun and dripping the perovskite precursor solution on one surface of a transparent electrode deposited electron transport layer, starting spin coating, absorbing 70 mu L of chlorobenzene by using the liquid transfer gun and dripping the chlorobenzene on the surface of the transparent electrode 7s before the spin coating is finished, and after the spin coating is finished, placing the transparent electrode on a heating table at 100 ℃ and annealing for 30min, wherein the perovskite layer is deposited on the electron transport layer of the transparent electrode;
s4, mixing 520mg of Li-TFSI powder with 1ml of acetonitrile to obtain a Li-TFSI solution with the concentration of 500-520 mg/ml, mixing 72.3mg of Spiro-OMeTAD powder, 28.8 mu L of 4-tert-butylpyridine, 17.5 mu L of Li-TFSI solution and 1ml of chlorobenzene, and uniformly stirring to obtain a Spiro-OMeTAD precursor solution; the transparent electrode processed at step S4 was placed on a spin coater, the spin speed of which was set to 3000r/m, the spin time was set to 30S, and the spin acceleration was set to 500r/m2Sucking 60 mu L of the Spiro-OMeTAD precursor solution by using a liquid transfer gun, dropwise adding the Spiro-OMeTAD precursor solution to one surface of a transparent electrode deposited perovskite layer, starting spin coating, placing the transparent electrode in a culture dish after the spin coating is finished, and depositing a hole transport layer on the perovskite layer of the transparent electrode;
s5 transferring the transparent electrode into a vacuum thermal evaporation device and placing in a mask plate, scraping off one electrode of spin coating, placing in a vapor deposition machine for thermal vapor deposition, vacuumizing the vapor deposition machine to below 106Torr, and starting to perform vacuum evaporation
When the thickness of the electrode reaches 100nm, stopping evaporation, and cooling for 1h to obtain the perovskite solar cell.
Example 2
As shown in fig. 1, the embodiment provides a photonic crystal modified perovskite solar cell, which sequentially includes a transparent electrode 100, an electron transport layer 300, a perovskite layer 400, a hole transport layer 500, and a counter electrode 600 from top to bottom, and further includes a photonic crystal layer 200, where the photonic crystal layer 200 is disposed between the transparent electrode 100 and the electron transport layer 300.
The preparation method of the perovskite solar cell modified by the photonic crystal comprises the following steps:
s1, etching the transparent electrode according to the schematic diagram of the etching area of FIG. 2 by using a diamond pen, placing the transparent electrode and the polytetrafluoroethylene cleaning frame on a polytetrafluoroethylene cleaning frame, then placing the etched transparent electrode and the polytetrafluoroethylene cleaning frame into a beaker, pouring isopropanol into the beaker until the transparent electrode is immersed, carrying out ultrasonic cleaning for 30min at the ultrasonic power of 40-60% at 20-25 ℃, then pouring out waste liquid, then adding detergent and deionized water, carrying out ultrasonic cleaning for 30min at the same ultrasonic power and temperature, then pouring out the waste liquid, adding deionized water, carrying out ultrasonic cleaning for 30min at the same ultrasonic power and temperature, repeatedly cleaning for 3 times, and then placing the electrode into a drying oven for drying for 12 h;
s2, soaking the transparent electrode processed in the step S1 in piranha solution for 2 hours, washing with deionized water, drying in a nitrogen environment, putting into a suspension of polystyrene monodisperse spheres dispersed in absolute ethyl alcohol, keeping heating in a drying furnace at 58 ℃ for 15 hours until volatile matters in the suspension are completely evaporated, and preparing a template of a polystyrene photonic crystal, namely a photonic crystal layer, on the transparent electrode; the piranha solution is a mixed solution of concentrated sulfuric acid with the concentration of more than 95% and hydrogen peroxide solution with the concentration of 30%, and the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide solution is 3: 1; the volume ratio of the polystyrene monodisperse spheres to the absolute ethyl alcohol in the suspension is 3: 8;
s3 the transparent electrode treated in step S2 was subjected to ozone treatment, and 1.5ml of 15% wt SnO2The solution was mixed with 6.5ml of deionized water to obtain SnO for preparing electron transport layers2The transparent electrode after ozone treatment is placed on a spin coater, the spin speed of the spin coater is set to 2000r/m, the spin time is set to 15s, and the spin acceleration is set to 500r/m260 mu L of SnO for preparing electron transport layer is dripped on the surface of the transparent electrode2Spin coating is carried out after the solution is dissolved, after the spin coating is finished, the transparent electrode is placed on a heating table at 150 ℃ for annealing for 15min, and the electron transmission layer is deposited on the photonic crystal layer on the transparent electrode;
s4, mixing 0.3260g of lead iodide powder, 0.0087g of cesium iodide powder and 0.1089g of FAI powder to obtain a powder mixture, mixing anhydrous DMSO and anhydrous DMF in a volume ratio of 1:4 to obtain a mixed solution, uniformly mixing 5.33ml of the mixed solution with the powder mixture, placing the mixed solution and the powder mixture at 70 ℃ while stirring and heating for 12 hours to obtain a perovskite precursor solution, and filtering the perovskite precursor solution through a filter head; subjecting the transparent electrode processed in step S3 to ozone treatment for 30min, placing on a spin coater in a glove box filled with Ar gas, setting the spin speed of the spin coater to 2000r/m, the spin time to 15S, and the spin acceleration to 500r/m2Absorbing 60 mu L of perovskite precursor solution by using a liquid transfer gun and dripping the perovskite precursor solution on one surface of a transparent electrode deposited electron transport layer, starting spin coating, absorbing 70 mu L of chlorobenzene by using the liquid transfer gun and dripping the chlorobenzene on the surface of the transparent electrode 7s before the spin coating is finished, and after the spin coating is finished, placing the transparent electrode on a heating table at 100 ℃ and annealing for 30min, wherein the perovskite layer is deposited on the electron transport layer of the transparent electrode;
s5, mixing 520mg of Li-TFSI powder with 1ml of acetonitrile to obtain a Li-TFSI solution with the concentration of 500-520 mg/ml, mixing 72.3mg of Spiro-OMeTAD powder, 28.8 mu L of 4-tert-butylpyridine, 17.5 mu L of Li-TFSI solution and 1ml of chlorobenzene, and uniformly stirring to obtain a Spiro-OMeTAD precursor solution; the transparent electrode processed in step S4 was placed on a spin coater, the spin speed of the spin coater was set to 2000r/m, the spin time was set to 15S, and the spin acceleration was setIs set to be 500r/m2Sucking 60 mu L of the Spiro-OMeTAD precursor solution by using a liquid transfer gun, dropwise adding the solution to one surface of a transparent electrode on which a perovskite layer is deposited, starting spin coating, placing the transparent electrode in a culture dish after the spin coating is finished, and depositing a hole transport layer on the perovskite layer of the transparent electrode;
s6 transferring the transparent electrode into vacuum thermal evaporation equipment and placing it into a mask plate, scraping off one electrode of spin coating, placing it into a deposition machine for thermal deposition, vacuumizing the deposition machine to below 106Torr, and starting to evaporate the transparent electrode
The evaporation rate is adopted for evaporation, when the thickness of the electrode is 100nm, the evaporation is stopped, and the perovskite solar cell modified by the photonic crystal is obtained after cooling for 1 h.
Example 3
The embodiment provides a perovskite solar cell modified by photonic crystal, which sequentially comprises a transparent electrode 100, an electron transport layer 300, a perovskite layer 400, a hole transport layer 500 and a counter electrode 600 from top to bottom, and further comprises a photonic crystal layer 200, wherein the photonic crystal layer 200 is arranged between the transparent electrode 100 and the electron transport layer 300.
The preparation method of the perovskite solar cell modified by the photonic crystal comprises the following steps:
s1, etching the transparent electrode according to the schematic diagram of the etching area of FIG. 2 by using a diamond pen, placing the transparent electrode and the polytetrafluoroethylene cleaning frame on a polytetrafluoroethylene cleaning frame, then placing the etched transparent electrode and the polytetrafluoroethylene cleaning frame into a beaker, pouring isopropanol into the beaker until the transparent electrode is immersed, carrying out ultrasonic cleaning for 30min at the ultrasonic power of 40-60% at 20-25 ℃, then pouring out waste liquid, then adding detergent and deionized water, carrying out ultrasonic cleaning for 30min at the same ultrasonic power and temperature, then pouring out the waste liquid, adding deionized water, carrying out ultrasonic cleaning for 30min at the same ultrasonic power and temperature, repeatedly cleaning for 3 times, and then placing the electrode into a drying oven for drying for 12 h;
s2, placing the transparent electrode processed in the step S1 into a piranha solution, soaking for 2 hours, washing with deionized water, drying in a nitrogen environment, placing into a suspension of polystyrene monodisperse spheres dispersed in absolute ethyl alcohol, keeping heating at 58 ℃ in a drying furnace for 15 hours until volatile matters in the suspension are completely evaporated, and preparing a template of a polystyrene photonic crystal, namely a photonic crystal layer, on the transparent electrode; the piranha solution is a mixed solution of concentrated sulfuric acid with the concentration of more than 95% and hydrogen peroxide solution with the concentration of 30%, and the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide solution is 3: 1; the volume ratio of the polystyrene monodisperse spheres to the absolute ethyl alcohol in the suspension is 3: 8;
s3 the transparent electrode treated in step S2 was subjected to ozone treatment, and 1.5ml of 15% wt SnO2The solution was mixed with 6.5ml of deionized water to obtain SnO for preparing electron transport layers2The transparent electrode after ozone treatment is placed on a spin coater, the spin coating speed of the spin coater is set to 3000r/m, the spin coating time is set to 30s, and the spin coating acceleration is set to 500r/m260 mu L of SnO for preparing electron transport layer is dripped on the surface of the transparent electrode2Spin coating is carried out after the solution is dissolved, after the spin coating is finished, the transparent electrode is placed on a heating table at 150 ℃ to be annealed for 15min, and the electron transmission layer is deposited on the photonic crystal layer on the transparent electrode;
s4, mixing 0.3260g of lead iodide powder, 0.0087g of cesium iodide powder and 0.1089g of FAI powder to obtain a powder mixture, mixing anhydrous DMSO and anhydrous DMF in a volume ratio of 1:4 to obtain a mixed solution, uniformly mixing 5.33ml of the mixed solution and the powder mixture, placing the mixed solution and the powder mixture at 70 ℃ while stirring and heating for 12 hours to obtain a perovskite precursor solution, and filtering the perovskite precursor solution through a filter head; the transparent electrode treated in step S3 was subjected to ozone treatment for 30min and then placed on a spin coater in a glove box into which Ar gas was introduced, the spin speed of the spin coater was set to 3000r/m, the spin time was set to 30S, and the spin acceleration was set to 500r/m2Absorbing 60 mu L of perovskite precursor solution by using a liquid transfer gun and dripping the perovskite precursor solution on one surface of a transparent electrode deposition electron transport layer, starting spin coating, absorbing 70 mu L of chlorobenzene by using the liquid transfer gun and dripping the chlorobenzene on the surface of the transparent electrode 7s before the spin coating is finished, and after the spin coating is finished, dripping the chlorobenzene on the surface of the transparent electrodeAnnealing the transparent electrode on a heating table at 100 ℃ for 30min, wherein the perovskite layer is deposited on the electron transport layer of the transparent electrode;
s5, mixing 520mg of Li-TFSI powder with 1ml of acetonitrile to obtain a Li-TFSI solution with the concentration of 500-520 mg/ml, mixing 72.3mg of Spiro-OMeTAD powder, 28.8 mu L of 4-tert-butylpyridine, 17.5 mu L of Li-TFSI solution and 1ml of chlorobenzene, and uniformly stirring to obtain a Spiro-OMeTAD precursor solution; the transparent electrode processed at step S4 was placed on a spin coater, the spin speed of which was set to 4000r/m, the spin time was set to 15S, and the spin acceleration was set to 500r/m2Sucking 60 mu L of the Spiro-OMeTAD precursor solution by using a liquid transfer gun, dropwise adding the Spiro-OMeTAD precursor solution to one surface of a transparent electrode deposited perovskite layer, starting spin coating, placing the transparent electrode in a culture dish after the spin coating is finished, and depositing a hole transport layer on the perovskite layer of the transparent electrode;
s6 transferring the transparent electrode into a vacuum thermal evaporation device and placing in a mask plate, scraping off one electrode of spin coating, placing in a vapor deposition machine for thermal vapor deposition, vacuumizing the vapor deposition machine to below 106Torr, and starting to perform vacuum evaporation
The evaporation rate is adopted for evaporation, when the thickness of the electrode is 100nm, the evaporation is stopped, and the perovskite solar cell modified by the photonic crystal is obtained after cooling for 1 h.
Example 4
The solar cells manufactured in examples 1 to 3 were placed under simulated sunlight and measured for their current density-voltage characteristic curves, i.e., J-V curves. The test light source is AM1.5G, 100mW cm-2The solar cell prepared in the embodiment 1 to 3 is placed under a test light source to irradiate for 3-5 min, and data are collected through a digital source meter. Important performance parameters that can be obtained by this test are: short-circuit current density Jsc, open-circuit voltage Voc, fill factor FF and photoelectric conversion efficiency PCE.
The test result chart is shown in fig. 3, wherein fig. 3(a), fig. 3(B) and fig. 3(C) are the test results of examples 1, 2 and 3, respectively, and it can be seen from the graph that the photoelectric conversion efficiency of example 2 is lower than that of example 3 because the spin coating parameters of example 2 and example 3 are different, and under the same preparation conditions, the solar cell thin film prepared by the spin coating parameters of example 3 is more dense and uniform, has higher photoelectric conversion efficiency and better stability.
In fig. 3, the photoelectric conversion efficiency of example 1 was the lowest because, compared to examples 2 and 3, which do not have a photonic crystal layer disposed between the transparent electrode and the electron transport layer, examples 1 and 2 prepared a polystyrene photonic crystal layer by an evaporation method under otherwise identical preparation conditions, the photonic crystal layer was uniformly dense and can modify SnO2The electron transport layer can improve the defect of the mesoporous framework quality of the electron transport layer, and particularly can improve SnO2The particle size avoids the problems of excessive grain boundary caused by over-small particles, serious carrier recombination and serious retardation during use, and meanwhile, the improved electron transport layer can reduce the defect density of the perovskite film and regulate and control the film forming quality of the perovskite layer, so that the prepared solar cell has better film quality and stability, and higher light absorption coefficient, photon-generated carrier separation efficiency and photoelectric conversion efficiency; moreover, as can be seen from the scanning electron microscope image of the polystyrene photonic crystal layer shown in fig. 4, the inside of the photonic crystal layer is of a honeycomb structure, so that light emitted by the scattering light source can pass through the transparent electrode and then be reflected and refracted for multiple times in holes of the honeycomb structure to reach the electron transport layer, the effect of enhancing the luminous intensity is achieved, the light energy is fully utilized, and the photoelectric conversion efficiency is improved substantially.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the claims of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. The perovskite solar cell modified by the photonic crystal comprises a transparent electrode, an electron transmission layer, a perovskite layer, a hole transmission layer and a counter electrode from top to bottom in sequence, and is further provided with a packaging structure; the interior of the photonic crystal layer is of a honeycomb structure.
2. The photonic crystal modified perovskite solar cell of claim 1, wherein the material of the transparent electrode is a base material doped with ITO, FTO, AZO or ATO, and the material of the electron transport layer is SnO2、TiO2、Nb2OS、SnO2、WO3、SrTiO3And Zn2SnO4The material of the perovskite layer is FAPBI3、MAPbI3The hole transport layer is made of Spiro-OMeTAD, CuI, CuSCN, NiO, CuO or Cu2O、CuGaO2、Cu2 NiOx、FeS2、MoS2、WS2、TiS2、Mg2Li2NiO, and the counter electrode is made of Au, Ag and Al.
3. A preparation method of a perovskite solar cell modified by photonic crystals is characterized by comprising the following steps:
s1, etching and ultrasonically cleaning the transparent electrode;
s2 preparing a photonic crystal layer on the transparent electrode processed in step S1;
s3 preparing an electron transport layer on the transparent electrode processed in step S2;
s4 preparing a perovskite layer on the electron transport layer prepared at step S3;
s5 preparing a hole transport layer on the perovskite layer prepared at step S4;
s6 preparing a counter electrode on the hole transport layer prepared at step S5 using a thermal evaporation method; the step S2 is: and (4) soaking the transparent electrode treated in the step (S1) in a piranha solution for 1-2 h, washing, drying in an inert gas environment, placing in a suspension of polystyrene monodisperse spheres dispersed in absolute ethyl alcohol, heating at 50-60 ℃ for 12-15 h until volatile matters in the suspension are completely evaporated, and then preparing a photonic crystal layer on the transparent electrode.
4. The method for preparing the photonic crystal modified perovskite solar cell according to claim 3, wherein the piranha solution is a mixed solution of concentrated sulfuric acid and a hydrogen peroxide solution, and the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide solution is (36): 1; the volume ratio of the polystyrene monodisperse spheres to the absolute ethyl alcohol in the suspension is (3-5): 8.
5. The preparation method of the photonic crystal modified perovskite solar cell according to claim 3, wherein the step S3 is to perform ozone treatment on the transparent electrode treated in the step S2, then 50-60 μ L of 10-15% wt SnO2 solution is dropwise added to the surface of the transparent electrode, spin coating is performed at a spin coating speed of 1000-3000 r/m for 15-30S, annealing is performed at 130-160 ℃ for 10-15 min, and the electron transport layer is deposited on the photonic crystal layer of the transparent electrode.
6. The preparation method of the photonic crystal modified perovskite solar cell according to claim 3, wherein the step S4 is to perform ozone treatment on the transparent electrode treated in the step S3, then dropwise add 50-60 μ L of perovskite precursor solution to one surface of the transparent electrode where the electron transport layer is deposited, spin-coat the transparent electrode at a spin-coating speed of 1000-3000 r/m for 15-30S, dropwise add 60-70 μ L of chlorobenzene on the surface of the transparent electrode before 5-8S after the spin-coating is finished, anneal the transparent electrode at 100 ℃ for 20-30 min after the spin-coating is finished, and the perovskite layer is deposited on the electron transport layer of the transparent electrode.
7. The method for preparing a photonic crystal modified perovskite solar cell according to claim 6, wherein the perovskite precursor solution is prepared by the following method: mixing lead iodide powder, cesium iodide powder and FAI powder according to a mass ratio of (30-40): 0-1): 8-11 to obtain a powder mixture, mixing anhydrous DMSO and anhydrous DMF according to a volume ratio of (1-2): 4 to obtain a mixed solution, mixing the powder mixture and the mixed solution 1 according to a mass ratio of (10-20), and heating the mixed solution for a period of time while stirring to obtain the perovskite precursor solution.
8. The method for preparing the photonic crystal modified perovskite solar cell according to claim 3, wherein in the step S5, a Spiro-OMeTAD precursor solution is dripped into the transparent electrode processed in the step S4, and after the transparent electrode is spin-coated for 10 to 20 seconds at a rotating speed of 2000 to 4000r/m, the hole transport layer is deposited on the perovskite layer of the transparent electrode.
9. The method for preparing a photonic crystal modified perovskite solar cell according to claim 8, wherein the Spiro-OMeTAD precursor solution is prepared by the following method: mixing Li-TFSI powder and acetonitrile to obtain a Li-TFSI solution with the concentration of 500-520 mg/ml, adding 4-tert-butylpyridine, the prepared Li-TFSI solution and chlorobenzene into the Spiro-OMeTAD powder, and uniformly stirring to obtain a Spiro-OMeTAD precursor solution; the mass ratio of the Li-TFSI powder to the Spiro-OMeTAD powder is (7-8): 1, and the volume ratio of the 4-tert-butylpyridine to the Li-TFSI solution to the chlorobenzene is (1-2): 1: (50-60).
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